Dispersion Forces Drive the Formation of Uranium-Alkane Adducts

Jung J, Löffler S, Langmann J, Heinemann FW, Bill E, Bistoni G, Scherer W, Atanasov M, Meyer K, Neese F (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Journal of the American Chemical Society American Chemical Society

DOI: 10.1021/jacs.9b10620

Abstract

Single-crystal cryogenic X-ray diffraction at 6 K, electron paramagnetic resonance spectroscopy, and correlated electronic structure calculations are combined to shed light on the nature of the metal-tris(aryloxide) and Ε2-H, C metal-alkane interactions in the [((t·BuArO)3tacn)UIII(Mecy-C6)]·(Mecy-C6) adduct. An analysis of the ligand field experienced by the uranium center using ab initio ligand field theory in combination with the angular overlap model yields rather unusual U-OArO and U-Ntacn bonding parameters for the metal-tris(aryloxide) interaction. These parameters are incompatible with the concept of σ and πmetal-ligand overlap. For that reason, it is deduced that metal-ligand bonding in the [((t·BuArO)3tacn)UIII] moiety is predominantly ionic. The bonding interaction within the [((t·BuArO)3tacn)UIII] moiety is shown to be dispersive in nature and essentially supported by the upper-rim tBu groups of the (t·BuArO)3tacn3- ligand. Our findings indicate that the axial alkane molecule is held in place by the guest-host effect rather than direct metal-alkane ionic or covalent interactions.

Authors with CRIS profile

Sascha Löffler Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Max-Planck-Institut für Kohlenforschung (MPI KoFo) / Max Planck Institute for Coal Research DE Germany (DE) Universität Augsburg DE Germany (DE) Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion DE Germany (DE)

How to cite

APA:

Jung, J., Löffler, S., Langmann, J., Heinemann, F.W., Bill, E., Bistoni, G.,... Neese, F. (2020). Dispersion Forces Drive the Formation of Uranium-Alkane Adducts. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b10620

MLA:

Jung, Julie, et al. "Dispersion Forces Drive the Formation of Uranium-Alkane Adducts." Journal of the American Chemical Society (2020).

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